WO1984001393A1 - Electrolytic copper plating solutions - Google Patents
Electrolytic copper plating solutions Download PDFInfo
- Publication number
- WO1984001393A1 WO1984001393A1 PCT/US1983/001508 US8301508W WO8401393A1 WO 1984001393 A1 WO1984001393 A1 WO 1984001393A1 US 8301508 W US8301508 W US 8301508W WO 8401393 A1 WO8401393 A1 WO 8401393A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogen
- alkali metal
- electroplating solution
- magnesium
- copper
- Prior art date
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 title claims abstract description 24
- 238000007747 plating Methods 0.000 title description 13
- 238000009713 electroplating Methods 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 239000011777 magnesium Substances 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 230000035939 shock Effects 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910006069 SO3H Inorganic materials 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- -1 alkali metal salt Chemical class 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 238000005282 brightening Methods 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 125000006353 oxyethylene group Chemical group 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229940069744 2,2'-dithiobisbenzothiazole Drugs 0.000 claims description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 3
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 claims 4
- 150000002431 hydrogen Chemical class 0.000 claims 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 3
- 125000004429 atom Chemical group 0.000 claims 2
- 229960002447 thiram Drugs 0.000 claims 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 0 C1C=CC=C2*=NNC12 Chemical compound C1C=CC=C2*=NNC12 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 125000005702 oxyalkylene group Chemical group 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- WIYCQLLGDNXIBA-UHFFFAOYSA-L disodium;3-(3-sulfonatopropyldisulfanyl)propane-1-sulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)CCCSSCCCS([O-])(=O)=O WIYCQLLGDNXIBA-UHFFFAOYSA-L 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- the invention relates to the electrodeposition of copper for decorative use and more particularly to the electrodeposition of copper on substrates having sharp corners such as formed by the holes drilled into copper clads for the production of printed circuit boards.
- Circuit boards are generally prepared by laminating copper clad to both sides of a plastic sheet such as an epoxy-glass. Holes are then drilled through the copper clad and the plastic, exposing the plastic. The exposed plastic must then be plated to effect conductivity from one side of the board to the other. This is generally accomplished by treating the plastic with an activator by well known processes, subjecting the entire circuit board to electroless deposition of copper to render the areas receptive to electrolytic copper depositions, and then plating the board and the internal surfaces of the holes by electrodeposition of copper. The sharp corners formed by the perimeter of the holes adjacent the top and bottom of the board must also be plated. This can be accomplished by many different copper electroplating solutions presently on the market, but the copper plate at the corners has a tendency to develop cracks when the boards are subjected to thermal shock necessitated by further processing of the boards.
- This invention relates to novel acid copper electroplating solutions containing the reaction product of a compound containing the structure
- R 1 , R 2 , R 3 and R 4 are as defined below, an alkylene disulfide having terminal acid groups and acrylamide.
- R 1 and R 2 are lower alkyl radicals of 1 to 6 carbon atoms, a hydrogen atom or mixtures thereof and R 4 an alkali metal, hydrogen, magnesium, or the groups SX or SSX where X is an alkali metal, hydrogen or magnesium, or
- R 3 is an aromatic, heterocyclic or alicyclic radical containing 3 to 12 carbon atoms and R 4 an alkali metal, hydrogen, magnesium, or the groups SX or SSX where X is an alkali metal, hydrogen or magnesium.
- the compounds found to be the most advantageous to date are the sodium salts of tetraalkylthiuram disulfide,
- R 1 and R 2 are methyl or ethyl or mixtures thereof , 2,2 '-dithio-bisbenzothiazole,
- the sodium salts of the compounds (3), (4) and (5) can readily be prepared by known means by heating the compounds dissolved in a solvent such as methanol (preferably with reflux) with sodium hydroxide.
- a solvent such as methanol (preferably with reflux) with sodium hydroxide.
- the compound of formulas (3), (4) and (5) are available commercially and marketed under the marks TUADS, ALTAX and CAPTAX, respectively, by R. T. Vanderbilt Company, Inc.
- the second reactant is an alkylene disulfide compound having terminal acid groups. These compounds correspond to the general formula
- R 1 and R 2 are the same or different and are alkylene radicals containing 1 to 6 carbon atoms
- X is hydrogen or -SO 3 H and n equals 2 to 5. Examples of a number of specific compounds coming within the scope of the above formula are set forth in column 2 of U.S. Patent 3,328,273 issued to Creutz et al. on June 27, 1967. It is preferable to use the alkali metal salts of the above compounds.
- alkylene disulfide di(sodium 3-sulfonate-1-propyl) sulfide
- the third reactant is acrylamide.
- reaction product(s) The exact chemical nature of the reaction product is not known.
- the products resulting from these reactions are hereinafter referred to as the reaction product(s).
- the invention includes the use of oxyalkylene polymers as brightening and leveling agents in combination with the reaction products.
- the oxyalkylene polymers have been found to materially increase the brightness and leveling of the deposits.
- the polyalkylene glycols such as polyethylene glycols, methoxy polyethylene glycols and the polypropylene glycols, have been found to be particularly advantageous.
- the oxyethylene or oxypropylene polymers can be surfactants, anionic, nonionic or cationic. Anionic and nonionic are preferred. These types of surfactants are well known and lists of specific polymers can be obtained by consulting any standard text on the subject such as the various volumes of Kirk-Othmer Encyclopedia of Chemical Technology or the industrial literature. It is the presence of the ethylene oxide or propylene oxide groups that is most important. The compounds should have at least about 8 mols of ethylene and/or propylene oxide and be soluble in the bath solution. Combinations of polyethylene and polypropylene glycols and/or surfactants can also be used.
- the amounts of the oxyalkylene polymers can be about the same as is usually employed in acid copper baths. A sufficient amount should, of course, be used to obtain the brightness and leveling desired which will in turn depend on the ultimate use intended. Generally about 0.1 to 0.5 g/1 or ml/1 can be employed.
- the copper deposited according to this invention is useful as decorative use, in the electronic industry generally, and for the conduction of electricity on substrates that do not have sharp corners or on articles where thermal shock is not a problem.
- the amounts of the reaction products employed in the acid copper plating solutions may therefore differ depending on the result desired, but in any event the amounts should be sufficient to improve the brightness and smoothness of the metallic deposits over that obtainable from the basic plating solutions.
- the amounts should be sufficient to prevent cracks in the deposit at the corners when the plated substrate is subjected to thermal shock. As far as it is known today, the amounts to accomplish both of these results will be substantially the same.
- the acid copper plating solutions to which the reaction products can be added are conventional and well known.
- the two essential constituents are a copper salt, such as copper sulfate, and an acid, such as sulfuric acid.
- the salt furnishes the metal ions and the acid serves to reduce the resistivity or promote conductivity.
- These baths typically contain between about 70-250 g/1 of copper sulfate and 30 to 250 g/1 of sulfuric acid.
- the reaction products can be formed by dissolving compounds of formulas (1) and/or (2), such as tetralakylthiuram disulfide sodium salt in a suitable solvent, adding a Bis(3-sulfoalkyl) disulfide salt to the reaction mixture together with acrylamide under reflux. Concentrated sulfuric acid is then added (dropwise in the laboratory) during the reflux and continued until gassing has ceased or no precipitate or turbidity is present.
- the reactants can be the mixtures as described above.
- the exact proportions of the reactants are not very critical but best results to date are obtained by using stoichiometric amounts.
- the reaction can include additional reactants so long as they do not affect the function and advantageous properties of the resulting reaction product.
- 0.6 g of formaldehyde can be added to the methanol solution and reacted with the sodium hydroxide before the addition of the disulfide compound and the resulting reaction product has substantially the same advantageous properties.
- a 2 gallon tank and a Hull cell was used on an acid copper plating solution of the following composition:
- the plating bath was operated at 75°F in a Hull cell with air agitation at a current of 2 amps for 10 minutes.
- the plating bath in the 2 gallon tank was operated at identical parameters, but at a current density of 15 ASF for an hour.
- Printed circuit boards with the holes drilled therein after being activated and electrolessly plated with copper were plated in this tank.
- the copper deposit on the circuit board was smooth and semi-lustrous over current density range of 2 to 20 ASF and showed no signs of corner cracks after thermal shock.
- Example 2 The procedure of Example 2 was followed except that the following material was also incorporated into the plating bath:
- Example 2 The procedure of Example 2 was followed except that the following materials were also incorporated into the plating bath:
- the deposit on the plated material was very bright and leveled in the current density range of from 1 to 100 ASF.
- the deposit on the printed circuit board plated in the 2 gallon tank was very bright and leveled and showed no signs of corner cracks after thermal shock.
- the thermal shock test to which the plated boards are subjected in the above examples is conventional. After the boards are baked for about an hour at 150°C, they are cooled to room temperature and allowed to float on one side in molten solder at 288°C for 10 seconds, then turned over and allowed to float on the solder on the other side for 10 seconds. The boards are then removed and inspected for cracks.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Chemically Coating (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42905582A | 1982-09-30 | 1982-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1984001393A1 true WO1984001393A1 (en) | 1984-04-12 |
Family
ID=23701587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1983/001508 WO1984001393A1 (en) | 1982-09-30 | 1983-09-28 | Electrolytic copper plating solutions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0107109B1 (enrdf_load_stackoverflow) |
| JP (1) | JPS59501829A (enrdf_load_stackoverflow) |
| AT (1) | ATE32611T1 (enrdf_load_stackoverflow) |
| DE (2) | DE3375732D1 (enrdf_load_stackoverflow) |
| WO (1) | WO1984001393A1 (enrdf_load_stackoverflow) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0163131A3 (en) * | 1984-04-27 | 1988-02-03 | Learonal, Inc. | An acid copper electroplating solution as well as a method of electroplating |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3721985A1 (de) * | 1987-06-30 | 1989-01-12 | Schering Ag | Waessriges saures bad zur galvanischen abscheidung glaenzender und eingeebneter kupferueberzuege |
| DE4032864A1 (de) * | 1990-10-13 | 1992-04-16 | Schering Ag | Saures bad zur galvanischen abscheidung von kupferueberzuegen und verfahren unter verwendung dieser kombination |
| DE19758121C2 (de) * | 1997-12-17 | 2000-04-06 | Atotech Deutschland Gmbh | Wäßriges Bad und Verfahren zum elektrolytischen Abscheiden von Kupferschichten |
| JP4115240B2 (ja) | 2002-10-21 | 2008-07-09 | 日鉱金属株式会社 | 特定骨格を有する四級アミン化合物及び有機硫黄化合物を添加剤として含む銅電解液並びにそれにより製造される電解銅箔 |
| DE10337669B4 (de) * | 2003-08-08 | 2006-04-27 | Atotech Deutschland Gmbh | Wässrige, saure Lösung und Verfahren zum galvanischen Abscheiden von Kupferüberzügen sowie Verwendung der Lösung |
| DE102005011708B3 (de) | 2005-03-11 | 2007-03-01 | Atotech Deutschland Gmbh | Polyvinylammoniumverbindung und Verfahren zu deren Herstellung sowie diese Verbindung enthaltende saure Lösung und Verfahren zum elektrolytischen Abscheiden eines Kupferniederschlages |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2888390A (en) * | 1956-11-08 | 1959-05-26 | Anaconda Co | Electrolytic refining of copper |
| US2954331A (en) * | 1958-08-14 | 1960-09-27 | Dayton Bright Copper Company | Bright copper plating bath |
| JPS4931183B1 (enrdf_load_stackoverflow) * | 1969-12-19 | 1974-08-20 | ||
| JPS4931406B1 (enrdf_load_stackoverflow) * | 1970-02-19 | 1974-08-21 | ||
| US4134803A (en) * | 1977-12-21 | 1979-01-16 | R. O. Hull & Company, Inc. | Nitrogen and sulfur compositions and acid copper plating baths |
| US4181582A (en) * | 1977-10-17 | 1980-01-01 | Schering Aktiengesellschaft | Galvanic acid copper bath and method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3328273A (en) * | 1966-08-15 | 1967-06-27 | Udylite Corp | Electro-deposition of copper from acidic baths |
-
1983
- 1983-09-28 WO PCT/US1983/001508 patent/WO1984001393A1/en unknown
- 1983-09-28 JP JP58503351A patent/JPS59501829A/ja active Granted
- 1983-09-30 AT AT83109814T patent/ATE32611T1/de not_active IP Right Cessation
- 1983-09-30 EP EP83109814A patent/EP0107109B1/en not_active Expired
- 1983-09-30 DE DE8383109814T patent/DE3375732D1/de not_active Expired
- 1983-09-30 DE DE198383109814T patent/DE107109T1/de active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2888390A (en) * | 1956-11-08 | 1959-05-26 | Anaconda Co | Electrolytic refining of copper |
| US2954331A (en) * | 1958-08-14 | 1960-09-27 | Dayton Bright Copper Company | Bright copper plating bath |
| JPS4931183B1 (enrdf_load_stackoverflow) * | 1969-12-19 | 1974-08-20 | ||
| JPS4931406B1 (enrdf_load_stackoverflow) * | 1970-02-19 | 1974-08-21 | ||
| US4181582A (en) * | 1977-10-17 | 1980-01-01 | Schering Aktiengesellschaft | Galvanic acid copper bath and method |
| US4134803A (en) * | 1977-12-21 | 1979-01-16 | R. O. Hull & Company, Inc. | Nitrogen and sulfur compositions and acid copper plating baths |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0163131A3 (en) * | 1984-04-27 | 1988-02-03 | Learonal, Inc. | An acid copper electroplating solution as well as a method of electroplating |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0107109A3 (en) | 1984-07-25 |
| ATE32611T1 (de) | 1988-03-15 |
| EP0107109B1 (en) | 1988-02-24 |
| JPS6250559B2 (enrdf_load_stackoverflow) | 1987-10-26 |
| JPS59501829A (ja) | 1984-11-01 |
| DE3375732D1 (en) | 1988-03-31 |
| EP0107109A2 (en) | 1984-05-02 |
| DE107109T1 (de) | 1985-02-14 |
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| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Designated state(s): JP |